Feed-through

ABSTRACT

A feed-through, for example a battery feed-through for a lithium-ion battery or a lithium ion accumulator, has at least one base body which has at least one opening through which at least one conductor, for example a pin-shaped conductor, embedded in a glass material is guided. The base body contains a low melting material, for example a light metal, such as aluminum, magnesium, AlSiC, an aluminum alloy, a magnesium alloy, titanium, titanium alloy or steel, in particular special steel, stainless steel or tool steel. The glass material consists of the following in mole percent: 35-50% P 2 O 5 , for example 39-48%; 0-14% Al 2 O 3 , for example 2-12%; 2-10% B 2 O 3 , for example 4-8%; 0-30% Na 2 O, for example 0-20%; 0-20% M 2 O, for example 12-20%, wherein M is K, Cs or Rb; 0-10% PbO, for example 0-9%; 0-45% Li 2 O, for example 0-40% or 17-40%; 0-20% BaO, for example 5-20%; 0-10% Bi 2 O 3 , for example 1-5% or 2-5%.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation of PCT application No. PCT/EP2012/000699,entitled “FEED-THROUGH”, filed Feb. 17, 2012, which is incorporatedherein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a feed-through, in particular a batteryfeed-through, in particular for a lithium-ion battery, for example alithium ion accumulator, a storage device, such as a battery, forexample a lithium-ion battery, as well as utilization of a glasscomposition for feed-through of a metallic conductor into the housing ofa battery, such as a lithium-ion battery.

2. Description of the Related Art

Integration of conductors, in particular in the form of metal pins intoa base body which consist of a light metal such as aluminum, hashitherto not been possible with battery feed-throughs.

Feed-throughs featuring thermally greatly expanding materials such asaluminum, aluminum alloys, copper and copper alloys have become knownonly in the field of high frequency feed-throughs (HF-feed-through).Such HF-feed throughs and glass materials on the basis ofaluminum-phosphate glasses are, for example, known from U.S. Pat. No.5,262,364; U.S. Pat. No. 5,965,469; as well as U.S. Pat. No. 6,037,539.

In particular U.S. Pat. No. 6,037,539 describes an HF-feed-throughwhereby a ferrous or respectively a non-ferrous conductor in analuminum-phosphate glass composition is inserted through a housingcomponent comprising aluminum. The HF-feed through known from U.S. Pat.No. 6,037,539 is substantially optimized for its purpose of application.Frequencies of between 8 and 1000 megahertz (MHz) are preferablytransferred with feed-throughs of this type. The high voltageapplication is also described in U.S. Pat. No. 6,037,539. However,battery feed-throughs are not described in U.S. Pat. No. 6,037,539.

Lithium-ion batteries have been known for many years. In this regard werefer you to the “Handbook of Batteries, published by David Linden, 2ndissue, McGrawhill, 1995, chapter 36 and 39”.

Various aspects of lithium-ion accumulators are described in a multitudeof patents, for example: U.S. Pat. No. 961,672; U.S. Pat. No. 5,952,126;U.S. Pat. No. 5,900,183; U.S. Pat. No. 5,874,185; U.S. Pat. No.5,849,434; U.S. Pat. No. 5,853,914; and U.S. Pat. No. 5,773,959.

In particular in the use of batteries, for example lithium-ionaccumulators in the automobile industry, a multitude of problems such ascorrosion resistance, stability in accidents or vibration resistancemust be solved. An additional problem is the hermetic seal of thebattery, in particular the lithium-ion battery over an extended periodof time. The hermetic seal may, for example, malfunction due to leakagein the area of the electrodes of the battery or respectively theelectrode feed-through of the battery, a battery short-circuit ortemperature changes, thus leading to a reduced life span of the battery.An additional problem with battery feed-throughs is the instability withrespect to the aggressive battery electrolytes, especially with respectto non-aqueous electrolytes as are used, for example, in lithium-ionaccumulators.

In order to ensure better stability in accidents, a housing for alithium-ion battery is suggested for example in DE 101 05 877 A1,whereby the housing includes a metal jacket which is open on both sidesand which is being sealed. The power connection is insulated by asynthetic material. A disadvantage of synthetic material insulations isthe limited temperature resistance, the uncertain hermetic seal over theservice life and the low chemical resistance with respect to the batteryelectrolytes.

What is needed in the art is a feed-through, in particular a batteryfeed-through, which avoids the problems of the current state of the art.

SUMMARY OF THE INVENTION

The present invention provides a feed-through, for example a batteryfeed-through, a storage device and a method of the use thereof.

A battery according to the present invention is to be understood to be adisposable battery which is disposed of and/or recycled after itsdischarge, as well as an accumulator. Exemplary materials discussed forlithium-ion accumulators are also light metal, in particular aluminum,an aluminum alloy or aluminum silicon carbide (AlSiC). Lithium-ionaccumulators are provided for various applications, for example forportable electronic equipment, cell phones, power tools and inparticular electric vehicles. The batteries can replace traditionalenergy sources, for example lead-acid batteries, nickel-cadmiumbatteries or nickel-metal hydride batteries.

According to a first aspect of the present invention a feed-through, forexample a battery feed-through for a lithium-ion battery, such as for alithium-ion accumulator is cited, having a base body whereby the basebody has at least one opening through which a conductor, in particular asubstantially pin-shaped conductor embedded in a glass material isguided, whereby the base body contains a material which has a lowmelting point, in particular a light metal, for example aluminum orAlSiC, aluminum alloys, magnesium or magnesium alloys. Also conceivableand covered by the invention are base bodies of titanium and/or titaniumalloys such as Ti 6246 and/or Ti 6242. Titanium is a material which iswell tolerated by the body, so that it is used for medical applications,for example in prosthetics. Due to its strength, resistance and lowweight its use is also favored in special applications, for example inracing sports, but also in aviation and aerospace applications.

Additional materials for the base body and/or the battery housing aremetals, especially steel, stainless steel, high-grade steel or toolsteel which is intended for a later heat treatment. Suitable for use ashigh-grade steels are, for example, X12CrMoS17, X5CrNi1810, XCrNiS189,X2CrNi1911, X12CrNi177, X5CrNiMo17-12-2, X6CrNiMoTi17-12-2, X6CrNiTi1810and X15CrNiSi25-20, X10CrNi1808, X2CrNiMo17-12-2, X6CrNiMoTi17-12-2. Inorder to be able to provide an especially effective weldability duringlaser welding as well as during resistance welding, high-grade steels,in particular Cr—Ni-steels having material grade numbers according toEuro-Norm (EN) 1.4301, 1.4302, 1.4303, 1.4304, 1.4305, 1.4306, 1.4307are used as materials for the base body and/or the housing component, inparticular the battery cell housing. St35, St37 or St38 can be used asstandard steel.

According to the present invention, the glass material through which theconductor is guided, includes at least the following components inmol-%:

P₂O₅ 35-50 mol-%, for example 39-48 mol-%; Al₂O₃ 0-14 mol-%, for example2-12 mol-%; B₂O₃ 2-10 mol-%, for example 4-8 mol-%; Na₂O 0-30 mol-%, forexample 0-20 mol-%; M₂O 0-20 mol-%, for example 12-20 mol-%, whereby M =K, can be Cs, Rb; PbO 0-10 mol-%, for example 0-9 mol-%; Li₂O 0-45mol-%, for example 0-40 mol-%, or 17-40 mol-%; BaO 0-20 mol-%, forexample 0-20 mol-%, or 5-20 mol-%; and Bi₂O₃ 0-10 mol-%, for example 1-5mol-%, or 2-5 mol-%.

Further, the glass material feed-through may have a composition whichincludes the following components:

P₂O₅ 38-50 mol-%, for example 39-48 mol-%; Al₂O₃ 3-14 mol-%, for example4-12 mol-%; B₂O₃ 4-10 mol-%, for example 5-8 mol-%; Na₂O 10-30 mol-%,for example 14-20 mol-%; K₂O 10-20 mol-%, for example 12-19 mol-%; andPbO 0-10 mol-%, for example 0-9 mol-%.

The listed inventive glass compositions are generally stable phosphateglasses which have a lower overall alkaline content thanalkali-phosphate glasses known from the current state of the art.

Surprisingly, it has been shown that the inventive glass compositionwith a lithium-share (Li-share) of up to 45 mol-%, for example 35 mol-%are crystallization-stable, meaning they do no display detrimentalcrystallization during a subsequent sintering process. It is furthernoted that a glass composition having up to 35 mol-% Li₂O does not showsignificant crystallization.

Because of the generally high crystallization-stability of the phosphateglasses it is ensured that melting of the glasses is generally nothampered even at temperatures of <600° C. This allows for most of thelisted glass compositions to be used as glass solder or fusible glassfor use with temperature sensitive materials and/or components, sincemelting of the glass compositions is generally not hampered even attemperatures of <600° C.

The listed glass compositions distinguish themselves in that the glassmaterials have a very high thermal expansion α in the range of 20° C. to300° C., which are in the range of >14×10⁻⁶/K, for example >15×10⁻⁶/K,or in the range of 15×10⁻⁶/K to 25×10⁻⁶/K and, therefore, in the rangeof the thermal expansion of light metals such as aluminum but also ofmetals commonly used for the conductors which are guided through theglass material, namely copper. Aluminum at room temperature has athermal expansion α of 23×10⁻⁶/K and copper of 16.5×10⁻⁶/K.

In order to avoid that the light metal of the base body and possiblyalso of the metal pin melts and deforms during sealing, the sealingtemperature for fusing of the glass material with the material of thebase body and/or the conductor is below the melting temperature of thematerial of the base body or conductor. The sealing temperature of thecited glass composition is in the range of 350° C. to 650° C. Thesealing temperature may, for example, be determined through thehemispherical temperature as described in R. Görke, K. J. Leers:Keram.Z.48 (1996) 300-305, or according to DIN 51730, ISO 540 or CEN/TS15404 and 15370-1 whose disclosure content is incorporated in itsentirety herein. The measurement of the hemispherical temperature isdescribed in detail in DE 10 2009 011 182 A1 whose disclosure content isincorporated in its entirety herein. According to DE 10 2009 011 182A1,the hemispherical temperature can be determined in a microscopic processby using a heating stage microscope. It identifies the temperature atwhich an originally cylindrical test body is melted into a hemisphericalmass. A viscosity of approximately log η=4.6 decipascal second (dPas)can be allocated to the hemispherical temperature, as can be learnedfrom appropriate technical literature. If a crystallization-free glass,for example in the form of a glass powder, is melted and then cooled sothat it solidifies, it can then normally be melted down again at thesame melting temperature. For a bonded connection with acrystallization-free glass this means that the operating temperature towhich the bonded connection is continuously subjected may not be higherthan the sealing temperature. Glass compositions as utilized in thecurrent application are generally often produced from a glass powderwhich is melted down and which, under the influence of heat provides thebonded connection with the components which are to be joined. Generally,the sealing temperature or melting temperature is consistent with thelevel of the so-called hemispherical temperature of the glass. Glasseshaving low sealing temperatures or respectively melting temperatures arealso referred to as solder glass. Instead of sealing or meltingtemperature, one speaks of solder temperature or soldering temperaturein this instance. The sealing temperature or respectively the soldertemperature may deviate from the hemispherical temperature by plus orminus 20K.

Sealing the conductor into the opening can then be accomplished asfollows: First, the glass material is inserted into the opening in thebase body, together with the pin shaped conductor. Then, the glasstogether with the conductor, for example a pin shaped conductor, isheated to the sealing temperature or respectively the hemisphericaltemperature of the glass, so that the glass material softens andenvelops the conductor, in particular the pin shaped conductor in theopening and fits closely against the base body. Since the meltingtemperature of the material of the base body as well as of theconductor, in particular the pin shaped conductor is higher than thesealing temperature of the glass, the base body, as well as the pinshaped conductor are in a solid state. The sealing temperature of theglass material is, for example, 20 to 150 K below the meltingtemperature of the material of the base body or respectively of the pinshaped conductor. If for example, the light metal used is aluminumhaving a melting point of T_(MELT)=660.32° C., then the fusingtemperature or respectively solder temperature of the glass material isin the range of between approximately 350° C. to 640° C., for example inthe range of 350° C. to <550° C., or in the range of 450° C. to <550° C.As an alternative to a light metal, such as for example aluminum or analuminum alloy, a silicon carbide (SiC) matrix which is infiltrated withAluminum (Al) could also be used as material for the base body. Amaterial of this type is also described as AlSiC. AlSiC has a SiC coreinto which Al is infused. Based on the proportion of Al the properties,especially the coefficient of expansion, can be adjusted. AlSiC notablyhas a lower heat expansion than pure aluminum.

Other materials which can be used for the base body and/or the batteryhousing are, for example, magnesium or magnesium alloys. The use oftitanium or titanium alloys is also conceivable for the base body. Alsometals, in particular steel, stainless steel, high-grade steel or toolsteel are conceivable materials.

The material of the conductor, for example the pin shaped conductor, canbe identical to the material of the base body—for example aluminum,Aluminum silicon carbide (AlSiC), an aluminum alloy, magnesium or amagnesium alloy. This has the advantage that the coefficient ofexpansion of the base body and the metal pin is identical. Thecoefficient of expansion α of the glass- or glass ceramic material needsthen only to be adapted to one material. Furthermore, the outerconductor may include high-grade steel or steel. In order to provide acompression seal feed-through in such a case, α_(base body) is selecteddifferent from α_(metal pin).

Alternatively, the pin shaped conductor may include copper (Cu), acopper alloy, Copper silicon carbide (CuSiC) or a nickel iron (NiFe)alloy, silver, a silver alloy, gold, a gold alloy, a copper core, thatis a NiFe jacket with an interior copper part, as well as a cobalt ironalloy as materials.

As aluminum or respectively aluminum alloy for the conductor, thefollowing may be utilized:

EN AW-1050 A; EN AW-1350; EN AW-2014; EN AW-3003; EN AW-4032; ENAW-5019; EN AW-5056; EN AW-5083; EN AW-5556; A EN AW-6060; and ENAW-6061.

As copper or respectively copper alloys for the conductor, the followingmay be utilized:

Cu-PHC 2.0070; Cu-OF 2.0070; Cu-ETP 2.0065; Cu-HCP 2.0070; and Cu-DHP2.0090.

In the case that the base body and the metal pin are formed of differentmaterials, α_(base body)≧α_(glass)≧α_(metal pin) for example applies.The different coefficient of expansions of the materials then permitcompression sealing, whereby a frictional connection is establishedbetween glass material and surrounding materials.

The battery feed-through of the present invention not only distinguishesitself in that sealing, for example compression sealing into a base bodyhaving a low melting temperature is possible, but also sufficientresistance with respect to the battery electrolytes is provided. Thepresent invention provides in particular a sufficient chemical stabilityin regard to non-aqueous and as a rule, aggressive battery electrolytes.Non-aqueous battery electrolytes consist typically of a carbonate, inparticular a carbonate mixture, for example a mixture ofethylene-carbonate or dimethyl-carbonate, whereby the aggressivenon-aqueous battery electrolytes include a conducting salt, for exampleconducting salt LiPF₆, for example in the form of a 1 molar solution.Surprisingly, the listed glass compositions have in addition to a highthermal coefficient of expansion in the range of (20° C.-300°C.)>14×10⁻⁶/K, for example between 15×10⁻⁶/K and 25×10⁻⁶/K, a lowsealing or respectively hemispherical temperature, and a sufficientresistance to the previously mentioned solid battery electrolytes.

The glass compositions for the battery feed-through of the presentinvention include, for example, lithium (Li) which is built into theglass structure. Since Li is also contained in the electrolyte as usedfor Li-ion storage devices, battery efficiency is hereby not impaired.

Low sodium or respectively sodium-free glass compositions may also beutilized, since the diffusion of the alkali-ions occurs in Na+>K+>Cs+sequence and since therefore low sodium or respectively sodium-freeglasses are especially resistant to electrolytes, for example thosewhich are used in Li-ion storage devices.

The resistance of the composition according to the present inventionagainst the battery electrolytes can be verified in that the glasscomposition in the form of a glass powder is ground to a granularity ofd50=10 micrometers (μm) and is stored in the electrolytes for apredetermined time period, for example one week. d50 means, that 50% ofall particles or granules of the glass powder are smaller than orequivalent to a diameter of 10 μm. As non-aqueous electrolyte, acarbonate mixture of ethylene-carbonate and dimethyl-carbonate is used,for example, at a ratio of 1:1 with a molar LiPF₆ as conducting salt.After the glass powder was exposed to the electrolyte, the glass powdercan be filtered off and the electrolyte be examined for glass elementswhich were leached from the glass. Herein it was demonstrated that withthe glasses used according to the present invention such leaching in theutilized composition ranges occurs surprisingly only to a limited extentof less than 20 mass percent; and that in special instances leaching of<5 mass percent is achieved at a thermal expansion α in a temperaturerange of 20° C. to 300° C.>14×10⁻⁶/K, for example between 15×10⁻⁶/K and25×10⁻⁶/K. An additional advantage of the glass composition according tothe present invention which finds use in a battery feed-through with oneor several pins, for example of aluminum or an aluminum alloy can beseen in that sealing of the glass with the surrounding light metal orrespectively the metal of the conductor is possible also in a gaseousatmosphere which is not an inert gas atmosphere. In contrast to thepreviously used method, a vacuum is also no longer necessary forAl-fusing. This type of fusing can rather occur under atmosphericconditions. For both types of sealing N₂ or Ar can be used as inert gas.As a pre-treatment for sealing, the metal is cleaned and/or etched, andif necessary is subjected to targeted oxidizing or coating.

During the process temperatures of between 300° C. and 600° C. are usedat heating rates of 0.1 to 30 Kelvin per minute (K/min) and dwell timesof 1 to 60 minutes.

The listed glass compositions surprisingly show a high chemicalstability relative to the, for example, non-aqueous electrolyte and atthe same time a high thermal coefficient of expansion. This issurprising especially because it is assumed that the glass becomesincreasingly unstable the higher the thermal coefficient. It istherefore surprising that in spite of the high coefficient of expansionand the low sealing temperature the listed glass compositions offer asufficient stability.

Also, with Na₂O contents of to 29 mole percent (mol-%), for example to20 mol-% very stable glasses are obtained.

The listed inventive glass compositions can be provided with fillers forthe purpose of expansion adaptation that is, for adaptation of thecoefficient of expansion.

In order to make the glass composition accessible for IR-heating, theaforementioned glasses can be provided with doping agents having anemission maximum in the range of infrared radiation, in particularIR-radiation of an IR-source. Examples of materials for this are Fe, Cr,Mn, Co, V, pigments. The thus prepared glass material can be heated bylocally targeted infrared radiation.

The present invention provides a battery lead-through which, in contrastto lead-throughs known from the current state of the art, in particularthose using synthetic material as sealing material, distinguishes itselfthrough a high temperature resistance, in particular temperature changeresistance. Moreover, a hermetic seal is also provided duringtemperature change, thus avoiding that liquid, in particular batteryliquid can emerge and/or moisture can penetrate into the housing. It isunderstood that with a hermetic seal the helium leakage rate is <1×10⁻⁸milibar liters per second (mbar ls⁻¹), for example <1·10⁻⁹ mbar ls⁻¹.

The battery feed-through moreover provides sufficient chemicalresistance, in particular compared to non-aqueous battery electrodes.

One pre-treatment measure to which the battery feed-through can besubjected is pickling.

In addition to the feed-through and in accordance with anotherembodiment of the present invention, an electric storage device, forexample a battery, such as a battery cell which is provided with afeed-through is provided. The housing consists, for example, of the samematerial as the base body, for example a light metal. For battery cellsthe base body may be part of the battery housing. The battery is, forexample, a lithium-ion battery.

Materials for the housing or respectively the base body may also bemetals such as steel, stainless steel, high-grade steel, light metals,for example titanium, titanium alloys, aluminum, aluminum alloys,magnesium or magnesium alloys without restriction thereto.

In the current application metals which have a specific weight of lessthan 5.0 kilograms per cubic decimeter (kg/dm³) are understood to belight metals. The specific weight of the light metals is, for example,in the range of 1.0 kg/dm³ to 3.0 kg/dm³.

If the light metals are additionally used as materials for theconductors, for example for the pin shaped conductor or the electrodeconnection component, then the light metals further distinguishthemselves through an electric conductivity in the range of 5×10⁶Siemens per meter (S·m⁻¹) to 50×10⁻⁶ S·m⁻¹.

When used in compression seal feed-throughs the coefficient of expansionα of the light metal for the range of 20° C. to 300° C. is moreover inthe range of 10×10⁻⁶/K to 30×10⁻⁶/K.

Light metals generally have a melting temperature in the range of 350°C. to 800° C.

The battery may have a non-aqueous electrolyte, for example a carbonatebasis, such as a carbonate mixture. The carbonate mixture can include anethylene-carbonate in a mixture with dimethyl-carbonate with aconducting salt, for example LiPF₆.

According to a third embodiment of the present invention, a glassmaterial including the following components in mol-% is provided forinsertion of a metallic conductor into the housing of a storage device:

P₂O₅ 35-50 mol-%, for example 39-48 mol-%; Al₂O₃ 0-14 mol-%, for example2-12 mol-%; B₂O₃ 2-10 mol-%, for example 4-8 mol-%; Na₂O 0-30 mol-%, forexample 0-20 mol-%; M₂O 0-20 mol-%, for example 12-20 mol-%, whereby M =K can be Cs, Rb; PbO 0-10 mol-%, for example 0-9 mol-%; Li₂O 0-45 mol-%,for example 0-40 mol-%, or 17-40 mol-%; BaO 0-20 mol-%, for example 5-20mol-%, or 5-20 mol-%; and Bi₂O₃ 0-10 mol-%, for example 1-5 mol-%, or2-5 mol-%.

Further, a glass material according to the present invention may includeincluding the following components in mol-%:

P₂O₅ 38-50 mol-%, for example 39-48 mol-%; Al₂O₃ 3-14 mol-%, for example4-12 mol-%; B₂O₃ 4-10 mol-%, for example 5-8 mol-%; Na₂O 10-30 mol-%,for example 14-20 mol-%; K₂O 10-20 mol-%, for example 12-19 mol-%; andPbO 0-10 mol-%, for example 0-9 mol-%,for insertion of a metallic conductor into the housing of a storagedevice, for example a battery, such as a lithium-ion battery. In oneembodiment of the present invention, the metallic conductor of thestorage device is a light metal, which can include aluminum, an aluminumalloy, copper or a copper alloy. The base body as well as the housingmay also consist of light metal, for example aluminum or an aluminumalloy.

BRIEF DESCRIPTION OF THE DRAWINGS

The above-mentioned and other features and advantages of this invention,and the manner of attaining them, will become more apparent and theinvention will be better understood by reference to the followingdescription of an embodiment of the invention taken in conjunction withthe accompanying drawing, wherein:

The FIGURE illustrates a feed-through according to the presentinvention.

The exemplification set out herein illustrates one embodiment of theinvention and such exemplification is not to be construed as limitingthe scope of the invention in any manner.

DETAILED DESCRIPTION OF THE INVENTION

Referring now to the drawing, there is shown a feed-through 1 accordingto the present invention. Feed-through 1 includes a metal pin 3 as aconductor, for example a pin shaped conductor which consists of amaterial, for example aluminum, an aluminum alloy, a copper alloy orcopper. Feed-through 1 further includes a base body 5 in the embodimentof a metal part consisting according to the present invention of a metalwhich has a low melting point, that is a light metal such as aluminum,an aluminum alloy, magnesium, a magnesium alloy, titanium or a titaniumalloy. Metal pin 3 is inserted through an opening 7 which leads throughbase body or metal part 5. Even though only the insertion of a singlemetal pin through the opening is illustrated, several metal pins couldbe inserted through the opening, without deviating from the presentinvention.

The outer contour of opening 7 can be round, but also oval. Opening 7penetrates through entire thickness D of base body 5, or respectivelymetal part 5. Metal pin 1 is sealed into glass material 10 and isinserted inside glass material 10 through opening 7 through base body 5.Opening 7 is introduced into base body 5 through a separation process,for example stamping. In order to provide a hermetic feed-through ofmetal pin 3 through opening 7, metal pin 3 is sealed into a glass plugformed of the glass material according to the present. A substantialadvantage of this production method is that even under increasedpressure upon the glass plug, for example a compression load, expulsionof the glass plug with metal pin from opening 7 is avoided. The sealingtemperature of the glass material according to the present inventionwith the base body is 20K to 100K below the melting temperature of thematerial of base body 5 and/or of the conductor, for example the pinshaped conductor.

Table 1 below illustrates eight exemplary embodiments (AB1-AB8) for theinventive glass compositions which are compared in Table 2 withcomparative glasses (VB1-VB9).

TABLE 1 Mol-% AB1 AB2 AB3 AB4 AB5 AB6 AB7 AB8 P₂O₅ 47.6 43.3 43.3 43.337.1 40.0 42.0 46.5 B₂O₃ 7.6 4.8 4.7 4.8 4.9 6.0 6.0 7.6 Al₂O₃ 4.2 8.68.7 2.0 2 12.0 12.0 4.2 Na₂O 28.3 17.3 15.0 16.0 28.3 K₂O 12.4 17.3 17.318.0 19.0 12.4 PbO 9.0 BaO 8.7 8.7 15.4 14 Li₂O 17.3 34.6 42.1 Bi₂O₃ 5 1Hemisphere 513 554 564 540 625 553 502 Temperapture (° C.) α(20-300° C.)19 16.5 14.9 13.7 14.8 16.7 16.0 19.8 (10⁻⁶/K) Tg (° C.) 325 375 354 369359 392 425 347 Density 2.56 3 3.02 2.63 [g/cm³] Leaching 18.7 14.117.66 12.63 1.47 3.7 29.01 8.43 In Ma-% Weight- 10.7 0.37 0.1 0.13 0.13n.b. 0.006/0.001 0.45/0.66 Loss (%) after 70 h in 70° C.- Water

In addition to leaching, the hydrolytic resistances of the individualglasses were also determined.

The hydrolytic resistance tests were conducted so that melted down glasssamples were produced (2×2 centimeters (cm), height: ˜0.5 cm) which werestored in 200 mililiters (mL) water at 25° C. (degrees Celsius) and 70°C. for 70 hours. Subsequently the material loss in weight-% wasdetermined and listed in the table.

Exemplary embodiment 1 (AB1) in Table 1 is suitable in particular foraluminum/aluminum sealing, that is sealing an aluminum pin as conductorinto a surrounding aluminum base body.

Exemplary embodiment 6 in Table 1 is, for example, suitable for Cu/Alglazing, that is sealing a copper pin in the embodiment of a conductorinto a surrounding aluminum base body.

Even though some of the exemplary embodiments indicate a coefficient ofexpansion which is too low for bonding with Cu it becomes clear that ahigh Li component can be dissolved in the molten mass without the glassbecoming unstable with a glass composition of this type.

Exemplary embodiments 7 and 8 (AB7 and AB8) distinguish themselves inthat they contain Bi₂O₃, in place of PbO, as is the case in exemplaryembodiment 6 (AB6).

Surprisingly it has been shown that the water resistance can be clearlyincreased by Bi₂O₃. For example, by introducing 1 mol-% Bi₂O₃ a 10-timeshigher hydrolytic resistance could be achieved in exemplary embodiment 8(AB8) compared to exemplary embodiment 1 (AB1) with essentially the samealkali content. This is surprising to the expert.

Bi₂O₃, can in particular also be used in place of PbO according toexemplary embodiment 6 (AB6). Since lead is environmentally harmful,glass compositions which, except for contaminants, are free of PbO, thatis where PbO can be set to 0 mol-%—are advantageous. In this application“free of, except for contaminants” means that less than 100 parts permillion (ppm), for example less than 10 ppm, or less than 1 ppm of therespective components, for example lead, are contained in the glass.

Table 2 below lists conventional glass compositions (VB1-VB9) which wereexamined in comparison to the aforementioned inventive exemplaryembodiments AB1 through AB8.

Tables 1 and 2 show the composition in mol-%, the transformationtemperature Tg as defined for example in “Schott Guide to Glass”, secondedition, 1996, Chapman & Hall, pages 18-21, the total leaching in masspercentage (Ma-%), the coefficient of expansion α in 10⁻⁶/K in the rangeof 20° C.-300° C., as well as the density in g/cm³. The total leachingis determined as described in the introductory section, meaning that theglass compositions were ground to glass powder having a d50=10 μmgranularity, and were exposed for one week to the electrolyte consistingof ethylene-carbonate/dimethyl-carbonate at a ratio 1:1, with 1 molarLiPF₆ in the form of conducting salt dissolved therein and after thistime were examined for glass components which were leached from theglass. “n.b.” in Table 1 denotes unknown properties.

TABLE 2 Comparison examples VB 1 VB 2 VB 3 VB 4 VB 5 VB 6 VB 7 VB 8 VB 9System SiO₂ SiO₂ SiO₂ SiO₂ P₂O₅ P₂O₅ P₂O₅ P₂O₅ P₂O₅ Composition [mol-%]SiO₂ 66.5 66.6 63.3 77.8 55.4 2.6 ZrO₂ 2.4 11.8 Al₂O₃ 9.3 10.4 1.0 3.38.4 5.5 12.8 4.0 7.4 B₂O₃ 4.0 7.3 4.1 9.4 31.2 1.7 MgO 4.0 4.4 3.3 4.320.5 2.9 BaO 3.8 1.5 2.5 0.2 7.0 7.8 La₂O₃ 1.3 Li₂O 0.6 K₂O 7.9 2.0 2.4P₂O₅ 5.3 6.8 29.3 59.7 50.5 CaO 12.3 9.6 4.7 1.6 7.9 8.1 Na₂O 9.1 7.00.5 SrO 11.3 F 1.0 0.6 54.7 PbO SnO 27.0 42.2 ZnO 8.9 Tg 720 716 508 562464 680 n.b. 462 n.b. Total leaching in Ma.-% 43.5 52.4 167.0 64.4 2.1127.6 50.2 18.8 1.9 α (20° C.-300° C.) 4.6 3.8 10.4 4.9 14.8 5.5 n.b.n.b. n.b. Density [g/cm³] 2.6 2.5 n.b. 2.3 3.7 2.8 n.b. 2.8 n.b.

The comparison examples VB1, VB2 and VB6 cited in Table 2 show atransformation temperature Tg which is too high and a thermalcoefficient of expansion α which is too low compared to the compositionsaccording to exemplary embodiments AB1-AB8. Comparison example VB3 doeshave a sufficiently low Tg, a better, however not sufficient coefficientof expansion α in the range of 20° C. to 300° C., and a high instabilitywith respect to the battery electrolytes. Comparison example VB4 shows afavorable Tg, however the resistance and the coefficient of expansion αare not sufficient. Comparison example VB5 shows an excellentresistance, the Tg is satisfactory, however the coefficient of expansionα is not sufficient.

Surprisingly, exemplary embodiments AB1-AB8 according to Table 1 show ahigh coefficient of expansion α according to the present invention, lowTg and high chemical resistance in the inventive composition range. Theinventive glass compositions thereby provide sealing glasses orrespectively fusible glasses or respectively solder glasses for batteryfeed-throughs, having a low process temperature, a sealing temperaturewhich is lower than the melting point of light metal, for examplealuminum, a high coefficient of expansion α and an excellent resistanceto battery electrolytes.

The current invention cites for the first time a feed-through for ahousing, in particular for a battery housing, for example for alithium-ion battery which can be integrated into housing components ofbattery cell housings consisting of a light metal, such as aluminum(Al), aluminum alloy, magnesium, magnesium alloy, titanium or titaniumalloy. However, steel or high-grade steel, in particular stainless steelare also conceivable as materials for the battery cell housing. In sucha case, the materials of, for example, a pin shaped conductor with headpart and, if necessary, the base body are selected and adaptedaccordingly.

With the feed-through component according to the present invention abattery housing can be provided which is hermetically sealed even whenthe battery housing is deformed, in contrast to plastic feed-throughswhich have a tendency toward cracking. On batteries with batteryhousings which are equipped with an inventive feed-through an especiallyhigh fire resistance is provided in the event of a vehicle accident.This is particularly relevant in the use of batteries, for exampleLi-ion batteries in automobiles.

While this invention has been described with respect to at least oneembodiment, the present invention can be further modified within thespirit and scope of this disclosure. This application is thereforeintended to cover any variations, uses, or adaptations of the inventionusing its general principles. Further, this application is intended tocover such departures from the present disclosure as come within knownor customary practice in the art to which this invention pertains andwhich fall within the limits of the appended claims.

What is claimed is:
 1. A feed-through, comprising: at least one basebody having at least one opening; a conductor; and a glass material,said conductor being embedded in said glass material and inserted intosaid at least one opening of said at least one base body, said glassmaterial including the following in mole percent (mol-%): P₂O₅ 35-50mol-%;  Al₂O₃ 0-14 mol-%; B₂O₃ 2-10 mol-%; Na₂O 0-30 mol-%; M₂O 0-20mol-%, wherein M is one of K, Cs and Rb; PbO 0-10 mol-%; Li₂O 0-45mol-%; BaO 0-20 mol-%; and Bi₂O₃ 1-5 mol-%.


2. The feed-through according to claim 1, wherein said glass materialincludes the following in mole percent (mol-%): P₂O₅ 39-48 mol-%;  Al₂O₃2-12 mol-%; B₂O₃  4-8 mol-%; Na₂O 0-20 mol-%; M₂O 12-20 mol-%;  PbO  0-9mol-%; Li₂O 0-40 mol-%; BaO 0-20 mol-%; and Bi₂O₃  1-5 mol-%.


3. The feed-through according to claim 2, wherein said glass materialincludes: Li₂O 17-40 mol-%; BaO 5-20 mol-%; and Bi₂O₃  2-5 mol-%.


4. The feed-through according to claim 1, wherein said feed-through is abattery feed-through.
 5. The feed-through according to claim 4, whereinsaid battery feed-through is for a lithium-ion battery.
 6. Thefeed-through according to claim 4, wherein said battery feed-through isfor a lithium ion accumulator.
 7. The feed-through according to claim 1,wherein said conductor is a substantially pin-shaped conductor.
 8. Thefeed-through according to claim 7, wherein said conductor includes onemetal.
 9. The feed-through according to claim 8, wherein said one metalis one of copper, copper silicon carbide (CuSiC), aluminum, aluminumsilicon carbide (AlSiC), magnesium, silver, gold, aluminum alloys,silver alloys, gold alloys and nickel-iron (NiFe) alloys.
 10. Thefeed-through according to claim 1, wherein said base body is formed froma material having a low melting temperature.
 11. The feed-throughaccording to claim 10, wherein said material having a low meltingtemperature is a light metal.
 12. The feed-through according to claim11, wherein said light metal is one of aluminum, magnesium, aluminumsilicon carbide (AlSiC), an aluminum alloy, a magnesium alloy, titanium,a titanium alloy and steel.
 13. The feed-through according to claim 12,wherein said steel is one of a high-grade steel, stainless steel andtool steel.
 14. The feed-through according to claim 1, wherein saidglass material includes: P₂O₅ 38-50 mol-%;  Al₂O₃ 3-14 mol-%; B₂O₃ 4-10mol-%; Na₂O 10-30 mol-%;  K₂O 10-20 mol-%; and PbO 0-10 mol-%.


15. The feed-through according to claim 14, wherein said glass materialincludes: P₂O₅ 39-48 mol-%; Al₂O₃  4-12 mol-%; B₂O₃  4-8 mol-%; Na₂O14-20 mol-%; K₂O 12-19 mol-%; and PbO  0-9 mol-%.


16. The feed-through according to claim 1, wherein said glass materialhas a coefficient of expansion α in a range of between approximately 20°C. and 300° C. of >14×10⁻⁶/K.
 17. The feed-through according to claim16, wherein said coefficient of expansion α in a range of betweenapproximately 20° C. and 300° C. is in a range of between approximately15×10⁻⁶/K and 25×10⁻⁶/K.
 18. The feed-through according to claim 1, saidglass material further comprises a plurality of additives within a rangeof an emission maximum of infrared radiation.
 19. The feed-throughaccording to claim 18, wherein said plurality of additives include iron(Fe), Chromium (Cr), Cobalt (Co) and Vanadium (V).
 20. The feed-throughaccording to claim 1, wherein said glass material is sealed with atleast one of said base body and said conductor under a normalatmosphere.
 21. The feed-through according to claim 20, wherein saidbase body is an aluminum base body soldered with an aluminum conductorunder said normal atmosphere.
 22. The feed-through according to claim 1,wherein said glass material has a high chemical resistance tonon-aqueous battery electrolytes.
 23. The feed-through according toclaim 22, wherein said glass material has a high chemical resistance tocarbonates.
 24. The feed-through according to claim 23, wherein saidcarbonates are carbonate mixtures with a conducing salt.
 25. Thefeed-through according to claim 24, wherein said carbonate mixtures witha conducing salt include lithium hexafluorophosphate (LiPF₆).
 26. Astorage device, comprising: a feed-through including: at least one basebody having at least one opening; a conductor; and a glass material,said conductor being embedded in said glass material and inserted intosaid at least one opening of said at least one base body, said glassmaterial including the following in mole percent (mol-%): P₂O₅ 35-50mol-%;  Al₂O₃ 0-14 mol-%; B₂O₃ 2-10 mol-%; Na₂O 0-30 mol-%; M₂O 0-20mol-%, wherein M is one of K, Cs and Rb; PbO 0-10 mol-%; Li₂O 0-45mol-%; BaO 0-20 mol-%; and Bi₂O₃ 1-5 mol-%.


27. The storage device according to claim 26, wherein the storage deviceis a battery.
 28. The storage device according to claim 27, wherein saidbattery is a lithium-ion battery.
 29. The storage device according toclaim 28, wherein the storage device is a lithium-ion accumulator. 30.The storage device according to claim 29, wherein said battery includesa non-aqueous electrolyte.
 31. The storage device according to claim 30,wherein said non-aqueous electrolyte is a carbonate.
 32. The storagedevice according to claim 31, wherein said carbonate is a carbonatemixture with a conducting salt.
 33. The storage device according toclaim 32, wherein said carbonate mixture includes ethylene-carbonate anddimethyl-carbonate.
 34. The storage device according to claim 33,wherein said carbonate mixture with said conducting salt is LiPF₆. 35.The storage device according to claim 34, further comprising a housingaccommodating said feed-through.
 36. The storage device according toclaim 35, wherein said housing is a battery housing.
 37. The storagedevice according to claim 35, wherein said base body is one of a metal,a high-grade steel, stainless steel and a light metal.
 38. The storagedevice according to claim 37, wherein said base body is one of aluminum,aluminum silicon carbide (AlSiC), an aluminum alloy, magnesium, amagnesium alloy, titanium and a titanium alloy.
 39. The storage deviceaccording to claim 35, wherein said housing includes one of a metal, ahigh-grade steel, stainless steel and a light metal.
 40. The storagedevice according to claim 39, wherein said housing includes one ofaluminum, Al SiC, an aluminum alloy, magnesium, a magnesium alloy,titanium and a titanium alloy.
 41. A method of utilizing a glasscomposition, the method comprising the step of providing a batteryincluding a non-aqueous electrolyte; and using the glass composition toinsert a conductor into a housing of a battery, the glass compositionincluding: P₂O₅ 35-50 mol-%;  Al₂O₃ 0-14 mol-%; B₂O₃ 2-10 mol-%; Na₂O0-30 mol-%; M₂O 0-20 mol-%, wherein M is one of K, Cs and Rb; PbO 0-10mol-%; Li₂O 0-45 mol-%; BaO 0-20 mol-%; and Bi₂O₃ 1-5 mol-%.


42. The method according to claim 41, wherein the glass compositionincludes: P₂O₅ 39-48 mol-%;  Al₂O₃ 2-12 mol-%; B₂O₃  4-8 mol-%; Na₂O0-20 mol-%; M₂O 12-20 mol-%, wherein M is one of K, Cs and Rb; PbO  0-9mol-%; Li₂O 0-40 mol-%; BaO 0-20 mol-%; and Bi₂O₃  1-5 mol-%.


43. The method according to claim 42, wherein said glass compositionincludes: Li₂O 17-40 mol-%; BaO 0-20 mol-%; and Bi₂O₃  2-5 mol-%.


44. The method according to claim 42, wherein said non-aqueouselectrolyte is a carbonate.
 45. The method according to claim 44,wherein said carbonate is a carbonate mixture with a conducting salt.46. The method according to claim 45, wherein said carbonate mixturewith a conducting salt includes LiPF₆.
 47. The method according to claim41, wherein said battery is a lithium-ion battery.
 48. The methodaccording to claim 41, wherein said battery is a lithium-ionaccumulator.
 49. The method according to claim 41, the glass compositionincluding: P₂O₅ 38-50 mol-%;  Al₂O₃ 3-14 mol-%; B₂O₃ 4-10 mol-%; Na₂O10-30 mol-%;  K₂O 10-20 mol-%; and PbO 0-10 mol-%.


50. The method according to claim 49, the glass composition including:P₂O₅ 39-48 mol-%; Al₂O₃  4-12 mol-%; B₂O₃  5-8 mol-%; Na₂O 14-20 mol-%;K₂O 12-19 mol-%; and PbO  0-9 mol-%.


51. The method according to claim 50, wherein the conductor includes onemetal.
 52. The method according to claim 51, wherein said one metal isone of aluminum, AlSiC, copper, CuSiC, magnesium, silver, gold, analuminum alloy, a magnesium alloy, a copper alloy, a silver alloy, agold alloy and a NiFe alloy.
 53. The method according to claim 52,wherein said base body includes one of a light metal, a high-gradesteel, steel and stainless steel.
 54. The method according to claim 53,wherein said base body includes one of aluminum, AlSiC, an aluminumalloy, magnesium, a magnesium alloy, titanium, and a titanium alloy.